BACKGROUND OF THE INVENTION
1. Field of the Invention
[0001] Aspects of the present invention relate to a photosensitive paste composition, barrier
ribs for a plasma display panel (PDP) prepared using the composition, and a PDP including
the barrier ribs. More particularly, aspects of the present invention relate to a
photosensitive paste composition that makes it possible to prepare a barrier rib pattern
for a high-resolution and high-precision PDP through a single light exposure and to
provide barrier ribs having higher reflectance compared to conventional barrier ribs,
barrier ribs for a PDP prepared using the composition, and a PDP including the barrier
ribs.
2. Description of the Related Art
[0002] In a plasma display panel (PDP) structure, barrier ribs are formed on a lower panel
(or rear substrate) to secure a discharge space and to inhibit electrical and optical
cross-talk between neighboring cells. The pattern of the barrier ribs varies according
to the type of the PDP, and may be a stripe-type or a matrix-type. The barrier ribs
may also have various sizes (width and pitch).
[0003] Barrier ribs may be formed using a sand blasting method, an etching method or a photolithographic
method after forming an address electrode on a lower panel and a dielectric material
on the address electrode.
[0004] Regarding photolithography, a method of forming barrier ribs through a single light
exposure process by minimizing the difference between the refractive indexes of organic
and inorganic components in order to reduce reflection and scattering at the interface
between the organic and inorganic components was disclosed in
U.S. Patent No. 6,197,480.
U.S. Patent No. 6,117,614 discloses a method of inhibiting oxygen from adversely affecting crosslinking reactions
by minimizing the difference between refractive indexes of organic and inorganic components
as described in
U.S. Patent No. 6,197,480, and using chemically amplified type crosslinking using a photo-acid generator.
[0005] According to those disclosed photolithographic methods, a barrier rib having a high-resolution
can be manufactured more simply compared to a barrier rib manufactured by sand blasting.
However, the photolithographic methods described above have fundamental disadvantages.
While a predetermined amount of powder of titania, alumina, yttria or zinc oxide is
used when using a sand blasting method or etching in order to improve reflexibility,
such powder cannot be used in the single exposure photolithographic method because
the powder has a very high refractive index so as to fails to minimize refractive
index of organic components and prevents transmission of ultraviolet rays which is
irradiated during the light exposure. Therefore, if such a powder is used in the photolithographic
methods described above, more than one exposure may be necessary.
SUMMARY OF THE INVENTION
[0006] Aspects of the present invention provide a photosensitive paste composition that
makes it possible to prepare a barrier rib pattern of a high-resolution and high-precision
plasma display panel (PDP) through a single light exposure and to provide barrier
ribs having higher reflectance compared to conventional barrier ribs, barrier ribs
for a PDP prepared using the composition, and a PDP including the barrier ribs.
[0007] According to an embodiment of the present invention, there is provided a photosensitive
paste composition comprising: a fluoride sol dispersed in an organic material; and
an inorganic material, wherein an average refractive index of the fluoride sol N
1 and an average refractive index of the inorganic material N
2 satisfy Mathematical Formula 1 below:
[0008] According to another aspect of the present invention, barrier ribs for a plasma display
panel (PDP) are prepared by patterning the photosensitive paste composition.
[0009] According to another aspect of the present invention, there is provided a plasma
display panel (PDP) comprising the barrier ribs.
[0010] Additional aspects and/or advantages of the invention will be set forth in part in
the description which follows and, in part, will be obvious from the description,
or may be learned by practice of the invention.
[0011] According to an aspect of the present invention there is provided a photosensitive
paste composition as set out in Claim 1. Preferred features of this aspect are set
out in Claims 2 to 19. According to an aspect of the present invention there is provided
barrier ribs as set out in any one of Claims 1 to 19. According to an aspect of the
present invention there is provided a plasma display panel as set out in Claim 20.
BRIEF DESCRIPTION OF THE DRAWINGS
[0012] These and/or other aspects and advantages of the invention will become apparent and
more readily appreciated from the following description of the embodiments, taken
in conjunction with the accompanying drawings of which:
FIG. 1 is a perspective view of a plasma display panel (PDP) according to an embodiment
of the present invention.
DETAILED DESCRIPTION OF THE EMBODIMENTS
[0013] Reference will now be made in detail to the present embodiments of the present invention,
examples of which are illustrated in the accompanying drawings, wherein like reference
numerals refer to the like elements throughout. The embodiments are described below
in order to explain the present invention by referring to the figures.
[0014] A photosensitive paste composition according to aspects of the present invention
includes: a fluoride sol dispersed in an organic material; and an inorganic material,
wherein an average refractive index of the fluoride sol N
1 and an average refractive index of the inorganic material N
2 satisfy Mathematical Formula 1 below:
[0015] The photosensitive paste composition according to aspects of the present invention
includes a fluoride sol that is distinguishable from conventional photosensitive paste
compositions. The fluoride sol is a sol in which particles of a fluoride compound
having a size of several to several tens of nanometers are dispersed in an organic
material. The fluoride compound may be dispersed in an organic material in a stable
state in which agglomeration or precipitation does not occur and may be mixed with
an inorganic material. Barrier ribs prepared using the photosensitive paste including
such a fluoride sol have improved brightness by increasing reflectance compared to
conventional photosensitive barrier ribs.
[0016] The fluoride may be represented by Chemical Formula 1 or 2 below:
Chemical Formula 1 M
aF
b
Chemical Formula 2 M
xM'
yF
z
wherein M and M' are one selected from the group consisting of alkali metals, alkali
earth metals and Si; and
a, b, x, y and z, which represent ratios of the number of atoms, are each independently
an integer of 1 to 4 and may be the same or different. In particular, M may be an
alkali earth metal and M' may be an alkali metal in order to increase the production
yield. Furthermore, M may be magnesium or calcium in terms of availability.
[0017] The fluoride sol may be prepared by a process including: preparing a mixture by mixing
a water solution of M or M' including a chloride, a nitrate (NO
3) salt, a sulfate (SO
4) salt, an acetate (CH
3CO
2) salt, or the like and a fluoride water solution including NaF, KF, NH
4K, HF, or the like; preparing a fluoride precursor by substituting water with an organic
solvent; and dispersing the fluoride precursor in the organic material. Meanwhile,
a silica sol water solution may further be introduced into the preparation of the
fluoride precursor to form a silica-fluoride mixture, and the stability of the fluoride
may be secured by the network between the silica and fluoride. In addition, a surface
modifier may further be added to the preparation of the fluoride precursor
[0018] The fluoride sol prepared by the above-described method may have an average particle
diameter of 1 to 60 nm, or more specifically 2 to 40 nm, or even more specifically
4 to 20 nm. Fluorides having an average particle diameter of less than 1 nm are not
easily prepared and are not easily dispersed uniformly in an organic material. If
the average particle diameter of the fluoride is greater than 60 nm, light transmittance
may be reduced since light is scattered during light exposure.
[0019] An average refractive index of the fluoride in the fluoride sol may be in the range
of 1.3 to 1.45, more particularly 1.3 to 1.4, and an average refractive index of the
fluoride sol prepared by dispersing the fluoride precursor in the organic material
may be in the range of 1.4 to 1.5. If the average refraction indices of the fluoride
and the fluoride sol are not within the range above, a photosensitive paste composition
satisfying the refraction range of Mathematical Formula 1 may not be easily prepared.
[0020] Herein, the term "average refractive index of the fluoride sol" refers to an average
refractive index of the fluoride not including a solvent. The refraction index of
the fluoride sol may be measured using various methods. Herein, the fluoride sol is
coated onto a transparent film or a glass substrate and dried at 80 to 120°C for several
to several tens of minutes to remove the solvent, and then the refraction index is
measured using a refractometer.
[0021] The transmittance of a fluoride sol having a thickness of 1 cm may be at least 50%
at 500 nm. If the transmittance is less than 50%, photosensitivity of the paste may
be decreased during the light exposure. The amount of the fluoride in the fluoride
sol may be in the range of 1 to 40 parts by volume based on 100 parts by volume of
the organic material. If the amount of the fluoride is less than the range above in
the fluoride sol, the reflectance improving efficiency of barrier ribs may be decreased.
On the other hand, if the amount of the fluoride is greater than the range above,
crosslinking may not sufficiently occur during the light exposure so as not to obtain
desired barrier ribs.
[0022] The following two conditions may be considered in the mixture of the fluoride sol
and the inorganic material. First, average refractive indices of the fluoride sol
and the inorganic material may be considered. In particular, the refractive indices
of the fluoride sol and the inorganic material may satisfy the relation of Mathematical
Formula 1 above, or more specifically, the relation of Mathematical Formula 2 below,
or even more specifically, the relation of Mathematical Formula 3 below.
[0023] If the average refractive indices of the fluoride sol and the inorganic material
do not meet the relation of Mathematical Formula 1, light transmittance may be decreased
so that barrier ribs cannot be formed through a single light exposure process. As
the relation between the average refractive indices of the fluoride sol and the inorganic
material is close to that of Mathematical Formula 3, photosensitivity can be improved,
and the straightness of a pattern of barrier ribs can be increased due to reduced
light scattering.
[0024] Next, besides the refraction index condition, the amount of the fluoride in the fluoride
sol based on the amount of the inorganic material in the photosensitive paste may
be considered. The amount of the fluoride may be in the range of 1 to 20 parts by
volume, or more specifically, 2 to 10 parts by volume, based on 100 parts by volume
of the inorganic material. If the amount of the fluoride is less than the range above,
reflectance improving efficiency of barrier ribs may be decreased. On the other hand,
if the amount of the fluoride is greater than the range above, sintering properties
of the inorganic material may be reduced.
[0025] Average thermal expansion coefficients (CTEs, α) of the fluoride and the inorganic
material may satisfy Mathematical Formula 4 below.
[0026] If the average thermal expansion coefficients of the fluoride and inorganic material
do not satisfy the relation of Mathematical Formula 4, the substrate may be seriously
distorted or collapse after a calcination process.
[0027] The average refractive index of the inorganic material in the photosensitive paste
composition according to aspects of the present invention may be in the range of 1.4
to 1.8, more particularly 1.5 to 1.8. If the average refractive index of the inorganic
material is not within the range above, the difference of refraction indices between
the inorganic material and the fluoride sol may be too large to form barrier ribs
through a single light exposure process.
[0028] The inorganic material includes a low melting point glass frit and a high melting
point glass frit. The low melting point glass frit in the inorganic material is sintered
during a calcination process to form dense barrier ribs, and the high melting point
glass frit prevents the structure of the barrier ribs from being collapsed during
the calcination process.
[0029] The particle shape of the low melting point glass frit is not limited, but may be
a spherical shape, since the spherical shape may have excellent filling rate and UV
ray transmittance. An average particle diameter of the low melting point glass frit
may have a median value D
50 of 2 to 5 µm, a minimum value D
min of 0.1 µm, and a maximum value D
max of 20 µm. If the median value is less than 2 µm, or the minimum value is less than
0.1 µm, printing properties may be deteriorated due to decreased dispersibility and
a desired pattern of the barrier ribs may not be obtained due to a high shrinkage
rate. If the median value is greater than 5 µm, or the maximum value is greater than
20 µm, density of the barrier ribs and straightness of the pattern of barrier ribs
may be decreased.
[0030] A softening temperature (Ts) of the low melting point glass frit may satisfy Mathematical
Formula 5 below.
[0031] If the softening temperature of the low melting point glass frit is less than the
sintering temperature - 80 °C, the pattern of the barrier ribs may collapse during
the calcination process. On the other hand, if the softening temperature is greater
than the sintering temperature, sintering may not appropriately occur.
[0032] The amount of the low melting point glass frit may be in the range of 70 to 100 parts
by volume based on 100 parts by volume of the inorganic material. If the amount of
the low melting point glass frit is less than the range above, sintering may not appropriately
occur during the calcination process.
[0033] The low melting point glass frit may be a complex oxide including at least three
oxides selected from the group consisting of oxides of Pb, Bi, Si, B, Al, Ba, Zn,
Mg, Ca, P, V, Mo and Te, but is not limited thereto. The low melting point glass frit
may be used alone or in a combination of two or more low melting point glass frits.
In particular, the low melting point glass frit may be a PbO-B
2O
3 based glass, a PbO-SiO
2-B
2O
3 based glass, a Bi
2O
3-B
2O
3 based glass, a Bi
2O
3-SiO
2-B
2O
3 based glass, a SiO
2-B
2O
3-Al
2O
3 based glass, a SiO
2-B
2O
3-BaO based glass, a SiO
2-B
2O
3-CaO based glass, a ZnO-B
2O
3-Al
2O
3 based glass, a ZnO-SiO
2-B
2O
3 based glass, a P
2O
5 based glass, a SnO-P
2O
5 based glass, a V
2O
5-P
2O
5 based glass, a V
2O
5-Mo
2O
3 based glass or a V
2O
5-P
2O
5-TeO
2 based glass. As used herein, "P
2O
5-based glass" and similar terms refer to glasses having at least the named component
(e.g. P
2O
5), but that can include other components (e.g. oxides). For example, a P
2O
5-based glass may include P
2O
5 in addition to other oxides.
[0034] The particle shape of the high melting point glass frit is not limited, but may be
a spherical shape, since the spherical shape may have excellent filling rate and UV
ray transmittance. An average particle diameter of the high melting point glass frit
may have a median value D
50 of 1 to 4 µm, a minimum value D
min of 0.1 µm, and a maximum value D
max of 20 µm. If the median value is less than 1 µm, or the minimum value is less than
0.1 µm, photosensitivity may be decreased and a desired pattern of the barrier ribs
may not be obtained due to a high shrinkage rate. If the median value is greater than
4 µm, or the maximum value is greater than 20 µm, density of the barrier ribs and
straightness of the pattern of barrier ribs may be decreased.
[0035] A softening temperature (Ts) of the high melting point glass frit may satisfy Mathematical
Formula 6 below.
[0036] If the softening temperature of the high melting point glass frit is less than the
sintering temperature + 20 °C, the pattern of the barrier ribs may collapse during
the calcination process.
[0037] The amount of the high melting point glass frit may be in the range of 0 to 30 parts
by volume based on 100 parts by volume of the inorganic material. If the amount of
the high melting point glass frit is greater than the range above, sintering may not
appropriately occur during the calcination process.
[0038] The high melting point glass frit may be a complex oxide including at least three
oxides selected from the group consisting of oxides of Si, B, Al, Ba, Zn, Mg, and
Ca, but is not limited thereto. The high melting point glass frit may be used alone
or in combination of two or more high melting point glass frits. In particular, the
high melting point glass frit may be a SiO
2-B
2O
3-BaO based glass, a SiO
2-B
2O
3-CaO based glass, a SiO
2-B
2O
3-MgO based glass, a SiO
2-B
2O
3-CaO-BaO based glass, a SiO
2-B
2O
3-CaO-MgO based glass, a SiO
2-Al
2O
3-BaO based glass, a SiO
2-Al
2O
3-CaO based glass, a SiO
2-Al
2O
3-MgO based glass, a SiO
2-Al
2O
3-BaO-CaO based glass or a SiO
2-Al
2O
3-CaO-MgO based glass.
[0039] The average refractive indices of the low melting point glass frit and the high melting
point glass frit are in the range of 1.5 to 1.8. In addition, an average refractive
index of the low melting point glass frit N
3 and an average refractive index of the high melting point glass frit N
4 satisfy Mathematical Formula 7 below, or more specifically, satisfy Mathematical
Formula 8 below, or even more specifically satisfy Mathematical Formula 9 below.
[0040] If the difference of the average refractive indices between the low melting point
glass frit and the high melting point glass frit is out of the range shown in Mathematical
Formula 7, light transmittance may be decreased so that barrier ribs cannot be formed
through a single light exposure process. As the relation between the average refractive
indices of the low melting point glass frit and the high melting point glass frit
is close to that of Mathematical Formula 9, photosensitivity can be improved, and
straightness of a pattern of barrier ribs can be increased due to reduced light scattering.
[0041] The organic material may comprise: a binder; a photoinitiator or a photo-acid generator;
and a crosslinking agent. Two types of organic materials may be used herein as the
organic material into which the fluoride sol is dispersed. The first type of organic
material includes an alkali-soluble binder A, a photoinitiator and a crosslinking
agent A. During photolithography, a crosslinking reaction is performed at a region
exposed to light and the region turns insoluble in an alkali developing solution.
The organic material may further include an additive to improve the paste properties
and a solvent to control viscosity.
[0042] The second type of organic material includes an alkali-soluble binder B, a photo-acid
generator and a crosslinking agent B. During photolithography, acid is generated at
a region exposed to light and a crosslinking reaction is performed during a subsequent
baking process. Then, the region turns insoluble in a developing solution. The organic
material may further include an additive to improve the paste properties and a solvent
to control viscosity.
[0043] The binder A of the first type of organic material may be an acryl-based resin having
a carboxyl group that permits development in an alkali developing solution and controls
paste properties according to compositional variation. The acryl-based resin having
a carboxyl group improves dispersibility of the inorganic material in the photosensitive
paste and also adjusts viscosity and elasticity in addition to permitting the development
in an alkali developing solution. The acryl-based resin having a carboxyl group may
be prepared by copolymerizing a monomer having a carboxyl group and a monomer having
an ethylenically unsaturated group.
[0044] The monomer having a carboxyl group may include at least one selected from the group
consisting of acrylic acid, methacrylic acid, fumaric acid, maleic acid, vinyl acetic
acid and anhydrides thereof. The monomer having an ethylenically unsaturated group
may include at least one selected from the group consisting of methyl acrylate, ethyl
acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate,
isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, allyl acrylate, phenyl
acrylate, benzyl acrylate, butoxyethyl acrylate, butoxytriethyleneglycol acrylate,
cyclohexyl acrylate, dicyclopentanyl acrylate, dicyclopentenyl acrylate, 2-ethylhexyl
acrylate, glycerol acrylate, glycidyl acrylate, isobornyl acrylate, isodecyl acrylate,
isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethyleneglycol
acrylate, methoxydiethyleneglycol acrylate, phenoxyethyl acrylate, stearyl acrylate,
1-naphthyl acrylate, 2-naphthyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl
acrylate, aminoethyl acrylate, and the compounds in which an acrylate moiety thereof
is substituted with methacrylate, styrene, α-methylstyrene, α-2-dimethylstyrene, 3-methylstyrene,
and 4-methylstyrene.
[0045] In addition, the binder A may be a copolymer having a cross-linkable group formed
by reacting the carboxyl group of the copolymer with a compound having an ethylenically
unsaturated group. The compound having an ethylenically unsaturated group may be acryloyl
chloride, methacryloyl chloride, allylchloride, glycidylacrylate, glycidylmethacrylate,
3,4-epoxycyclohexylmethyl acrylate, 3,4-epoxycyclohexylmethyl methacrylate, or the
like.
[0046] In addition, the binder A may be the copolymer alone or a mixture of the copolymer
and at least one selected the group consisting of cellulose, methyl cellulose, ethyl
cellulose, n-propyl cellulose, hydroxyethyl cellulose, 2-hydroxyethyl cellulose, methyl
2-hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose,
hydroxybutyl methyl cellulose, hydroxypropyl methyl cellulose phthalate, cellulose
nitrate, cellulose acetate, cellulose triacetate, cellulose acetate butyrate, cellulose
acetate hydrogen phthalate, cellulose acetate propionate, cellulose propionate, (acrylamidomethyl)cellulose
acetate propionate, (acrylamidomethyl)cellulose acetate butyrate, cyanoethylate cellulose,
pectic acid, chitosan, chitin, carboxymethyl cellulose, carboxymethyl cellulose sodium
salt, carboxyethyl cellulose, and carboxyethylmethyl cellulose in order to improve
membrane leveling or thixotropy characteristics.
[0047] A weight average molecular weight of the copolymer may be in the range of 500 to
100,000 g/mol, and an acid value may be in the range of 50 to 300 mgKOH/g. If the
weight average molecular weight of the copolymer is less than 500 g/mol, dispersity
of the inorganic material in the paste may be reduced. On the other hand, if the weight
average molecular weight of the copolymer is greater than 100,000 g/mol, development
speed may be too slow or development may not be performed. In addition, if the acid
value of the copolymer is less than 50 mgKOH/g, developing properties may be decreased.
On the other hand, if the acid value of the copolymer is greater than 300 mgKOH/g,
regions exposed to light may also be developed.
[0048] The amount of the binder A may be in the range of 30 to 80 parts by weight based
on 100 parts by weight of the organic material (the binder A, the photoinitiator and
the crosslinking agent). If the amount of the binder A is less than the range above,
coating properties of the paste and dispersity may be decreased. On the other hand,
if the amount of the binder A is greater than the range above, crosslinking may not
sufficiently occur during the light exposure so as not to obtain desired barrier ribs.
[0049] The photoinitiator generates radicals in response to light radiated by an light exposure
device, and the generated radicals initiate polymerization of the crosslinking agent
having an ethylenically unsaturated group to make the paste insoluble in a developing
solution. Since the photoinitiator requires high sensitivity, at least two photoinitiators
selected from the group listed below may be mixed and used. Examples of the photoinitiator
include (i) imidazole-based compounds, (ii) triazine-based compounds, (iii) aminoacetophenone-based
compounds, (iv) benzophenone and acetophenone-based compounds (v) benzoin-based compounds,
(vi) titanocene-based compounds, (vii) oxadiazole-based compounds, (viii) thioxanthone-based
compounds, (ix) (bis)acylphosphine oxide-based compounds, or (x) organic boron salt-based
compounds, but are not limited thereto.
[0050] The imidazole-based compound may be 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(o,p-dichlorophenyl)-1,2'-biimidazole,
2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetra(o,p-dichlorophenyl)-1,2'-biimidazole,
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)-1,2'-biimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole,
or the like.
[0051] The triazine-based compound may be 2,4,6-tris(trichloromethyl)-s-triazine, 2,4,6-tris(tribromomethyl)-s-triazine,
2-propionyl-4,6-bis(trichloromethyl)-s-triazine, 2-benzoyl-4,6-bis(trichloromethyl)-s-triazine,
2-(4-chlorophenyl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(4-methoxyphenyl)-6-trichloromethyl)-s-triazine,
2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine,
2-(4-chlorostyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-aminophenyl)-4,6-bis(trichloromethyl)-s-triazine,
2,4-bis(3-chlorophenyl)-6-trichloromethyl-s-triazine, 2-(4-aminostyryl)-4,6-bis(dichloromethyl)-s-triazine,
or the like.
[0052] The aminoacetophenone-based compound may be 2-methyl-2-amino(4-morpholinophenyl)ethane-1-one,
2-ethyl-2-amino(4-morpholinophenyl)ethane-1-one, 2-propyl-2-amino(4-morpholinophenyl)ethane-1-one,
2-butyl-2-amino(4-morpholinophenyl)ethane-1-one, 2-methyl-2-amino(4-morpholinophenyl)propane-1-one,
2-methyl-2-amino(4-morpholinophenyl)butane-1-one, 2-ethyl-2-amino(4-morpholinophenyl)propane-1-one,
2-ethyl-2-amino(4-morpholinophenyl)butane-1-one, 2-methyl-2-methylamino(4-morpholinophenyl)propane-1-one,
2-methyl-2-dimethylamino(4-morpholinophenyl)propane-1-one, 2-methyl-2-diethylamino(4-morpholinophenyl)propane-1-one,
or the like.
[0053] The benzophenone and acetophenone-based compound may be benzophenone, 4-methylbenzophenone,
2,4,6-trimethylbenzophenone, benzoylbenzoic acid, 4-phenylbenzophenone, 3,3'-dimethyl-4-methoxybenzophenone,
4-benzoyl-4'-methyldiphenylsulfide, 4,4'-bis(N,N-dimethylamino)benzophenone, 4,4'-bis(N,N-diethylamino)benzophenone,
3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, (2-acryloyloxyethyl)(4-benzoylbenzyl)dimethylammonium
bromide, 4-(3-dimethylamino-2-hydroxypropyl)benzophenone, (4-benzoylbenzyl)trimethylammonium
chloride, methochloride monohydrate, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1-one,
1-(4-isopropylphenyl)-2-methylpropane-1-one, 1-hydroxycyclohexylphenylketone, 4-tert-butyl-trichloroacetophenone,
or the like.
[0054] The benzoin-based compound may be benzoin, benzoinmethyl ether, benzoinethyl ether,
benzoinisopropyl ether, benzoinisobutyl ether, or the like.
[0055] The titanocene-based compound may be dicyclopentadienyl-Ti-dichloride, dicyclopentadienyl-Ti-diphenyl,
dicyclopentadienyl-Ti-bis(2,3,4,5,6-pentafluorophenyl), dicyclopentadienyl-Ti-bis(2,3,5,6-tetrafluorophenyl),
dicyclopentadienyl-Ti-bis(2,4,6-trifluorophenyl), dicyclopentadienyl-Ti-bis(2,6-difluorophenyl),
dicyclopentadienyl-Ti-bis(2,4-difluorophenyl), bis(methylcyclopentadienyl)-Ti-bis(2,3,4,5,6-pentafluorophenyl),
bis(methylcyclopentadienyl)-Ti-bis(2,3,5,6-tetrafluorophenyl), bis(methylcyclopentadienyl)-Ti-bis(2,4,6-trifluorophenyl),
bis(methylcyclopentadienyl)-Ti-bis(2,6-difluorophenyl), bis(methylcyclopentadienyl)-Ti-bis(2,4-difluorophenyl),
or the like.
[0056] The oxadiazole-based compound may be 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole,
2-(p-methylphenyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(p-methoxyphenyl)-5-trichloromethyl-1,3,4-oxadiazole,
2-styryl-5-trichloromethyl-1,3,4-oxadiazole, 2-(p-methoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole,
2-(p-butoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole, or the like.
[0057] The thioxanthone-based compound may be thioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone,
2,4-diisopropylthioxanthone, 2-chlorothioxanthone, 1-chloro-4-propoxythioxanthone,
2-(3-dimethylamino-2-hydroxypropoxy)-3,4-dimethyl-9H-thioxanthen-9-one methochloride,
or the like.
[0058] The (bis)acylphosphine oxide-based compound may be 2,4,6-trimethylbenzoyldiphenylphosphineoxide;
bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphineoxide, bis(2,6-dichlorobenzoyl)phenylphosphineoxide,
bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphineoxide, bis(2,4,6-trimethylbenzoyl)phenylphosphineoxide,
or the like.
[0059] The organic boron salt-based compound may be a quaternary organic boron salt represented
by Chemical Formula 6 below.
[0060] In Chemical Formula 6, R
1, R
2, R
3, and R
4 are each independently a substituted or unsubstituted alkyl group, aryl group, aralkyl
group, alkenyl group, alkynyl group, silyl group, or heterocyclic group, or a halogen
atom, and Z
+ is a cation. As specific, non-limiting examples, the substituent may be a methyl
group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a
sec-butyl group, an isobutyl group, a tert-butyl group, an n-octyl group, an n-decyl
group, an n-dodecyl group, a cyclopentyl group, a cyclohexyl group, a phenyl group,
a tolyl group, a xylyl group, an anisyl group, a biphenyl group, a diphenylmethyl
group, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, an
n-butoxy group, a sec-butoxy group, an isobutoxy group, a tert-butoxy group, methylenedioxy
group, ethylenedioxy group, phenoxy group, naphthoxy group, benzyloxy group, methylthio
group, phenylthio group, 2-furyl group, 2-thienyl group, 2-pyridyl group, fluorine
group, or the like.
[0061] As non-limiting examples, the quaternary organic boron anion of the organic boron
salt-based compound may be methyltriphenylborate, n-butyltriphenylborate, n-octyltriphenylborate,
n-decyltriphenylborate, n-dodecyltriphenylborate, sec-butyltriphenylborate, tert-butyltriphenylborate,
benzyltriphenylborate, n-butyltri(p-anisyl)borate, n-octyltri(p-anisyl)borate, n-dodecyltri(p-anisyl)borate,
n-butyltri(p-tolyl)borate, n-butyltri(o-tolyl)borate, n-butyltri(4-tert-butylphenyl)borate,
n-butyltri(4-fluoro-2-methylphenyl)borate, n-butyltri(4-fluorophenyl)borate, n-butyltri(1-naphthyl)borate,
ethyltri(1-naphthyl)borate, n-butyltri[1-(4-methylnaphthyl)]borate, methyltri[1-(4-methylnaphthyl)]borate,
triphenylsilyltriphenylborate, trimethylsilyltriphenylborate, tetra-n-butylborate,
di-n-butyldiphenylborate, tetrabenzylborate, or the like. For example, in the quaternary
organic boron anion, R
1 may be an alkyl group, R
2, R
3, and R
4 may be naphthyl groups in order to maintain stability of the compound and balance
of photoreactivity.
[0062] The cation Z
+ of the organic boron salt may be tetramethylammonium, tetraethylammonium, tetra-n-butylammonium,
tetraoctylammonium, N-methylquinolium, N-ethylquinolium, N-methylpyridinium, N-ethylpyridinium,
tetramethylphosphonium, tetra-n-butylphosphonium, trimethylsulfonium, triphenylsulfonium,
trimethylsulfoxonium, diphenyliodonium, di(4-tert-butylphenyl)iodonium, a lithium
cation, a sodium cation, a potassium cation, or the like.
[0063] The photoinitiator composition may further include a sensitizer to increase the sensitivity
of the photoinitiator. The sensitizer may vary according to the photoinitiator. A
photoinitiator may function as a sensitizer of another photoinitiator.
For example, if an imidazole-based photoinitiator is used, a benzophenone-based or
thioxanthone-based compound functions as not only a photoinitiator but also a sensitizer
of the imidazole-based photoinitiator. Any compound that can absorb light and degrade
the organic boron salt compound may be used as the sensitizer for the organic boron
salt. The compound may be a benzophenone-based compound, a thioxanthone-based compound,
a quinone-based compound, or a cationic dye. The benzophenone-based compound and the
thioxanthone-based compound are described above. The quinone-based compound may be
quinhydrone, 2,5-dichloro-1,4-benzoquinone, 2,6-dichloro-1,4-benzoquinone, phenyl-1,4-benzoquinone,
2-methyl-1,4-naphthoquinone, 2,3-dichloro-1,4-naphthoquinone, 2-hydroxy-1,4-naphthoquinone,
5-hydroxy-1,4-naphthoquinone, 2-amino-3-chloro-1,4-naphthoquinone, 2-chloro-3-morpholino-1,4-naphthoquinone,
anthraquinone, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone,
2,3-dimethylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,4-dichloroanthraquinone,
2-(hydroxymethyl)anthraquinone, 9,10-phenanthrenequinone, or the like. The cationic
dye generally has a maximum absorption wavelength in the range of 300 nm to near infrared
ray region. Thus, the cationic dye has yellow, orange, red, green or blue color, and
more particularly, Basic yellow 11, Astrazon orange G, Thioflavin T, Auramine O, Indocyanine
green, 1,1',3,3,3',3'-hexamethylindodicarbocyanine iodide, IR-786 perchlorate, or
the like.
[0064] The amount of the photoinitiator may be in the range of 1 to 20 parts by weight based
on 100 parts by weight of the organic material. If the amount of the photoinitiator
is less than the range above, the photosensitivity may be decreased. On the other
hand, if the amount of the photoinitiator is greater than the range above, regions
not exposed to the light may not be developed.
[0065] The crosslinking agent A may be a mono acrylate or a multifunctional acrylate. The
mono acrylate may be acrylic acid, methyl acrylate, ethyl acrylate, n-propyl acrylate,
isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl
acrylate, n-pentyl acrylate, allyl acrylate, phenyl acrylate, benzyl acrylate, butoxyethyl
acrylate, butoxytriethyleneglycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate,
dicyclopentenyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate,
isobornyl acrylate, isodecyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl
acrylate, methoxyethyleneglycol acrylate, methoxydiethyleneglycol acrylate, phenoxyethyl
acrylate, stearyl acrylate, 1-naphthyl acrylate, 2-naphthyl acrylate, 2-hydroxyethyl
acrylate, 2-hydroxypropyl acrylate, aminoethyl acrylate, and the compounds in which
an acrylate moiety thereof is substituted with methacrylate, but is not limited thereto.
The multifunctional acrylate may be: a diacrylate such as1,6-hexanediol diacrylate,
1,6-hexanediol(ethoxylate)diacrylate, 1,4-butanediol diacrylate, 2-butyl-2-ethyl-1,3-propanediol
diacrylate, 1,9-nonanediol diacrylate, tripropyleneglycol diacrylate, dipropyleneglycol
diacrylate, tetraethyleneglycol diacrylate, bisphenol A (ethoxylate)
n (n = 2 to 8) diacrylate, and bisphenol A epoxy diacrylate; a triacrylate such as
trimethylolpropane triacrylate, trimethylolpropane(ethoxylate)triacrylate, glycerin(propoxylate)triacrylate,
pentaerythritol triacrylate, and
trimethylolpropane(propoxylate)-3-triacrylate; a tetraacrylate such as ditrimethylolpropane
tetraacrylate, tetramethylolpropane tetraacrylate, and pentaerythritol tetraacrylate;
a pentaacrylate such as dipentaerythritol pentaacrylate; a hexaacrylate such as dipentaerythritol
hexaacrylate, or the compounds in which at least one acrylate moiety is substituted
with methacrylate, but is not limited thereto.
[0066] The amount of the crosslinking agent A may be in the range of 15 to 60 parts by weight
based on 100 parts by weight of the organic material. If the amount of the crosslinking
agent A is less than the range above, the photosensitivity may be decreased. On the
other hand, if the amount of the crosslinking agent A is greater than the range above,
the pattern of the barrier ribs may detached or disconnected during sintering.
[0067] The binder B of the second type of organic material improves the dispersibility of
the inorganic material in the photosensitive paste and also adjusts the viscosity
and elasticity in addition to permitting the development in an alkali developing solution.
The binder B may be a resin having a phenolic hydroxyl group, a resin having a hydroxystyrene
structure, a resin having an epoxy group or a resin having a hydroxyl group and a
carboxyl group, but is not limited thereto, and the resins may be used alone or in
a combination of two or more.
[0068] The resin having a phenolic hydroxyl group may be a novolak resin, which is prepared
by condensation-polymerization of a phenol and an aldehyde, or condensation-polymerization
of a phenol and a ketone in the presence of an acid. The resin having a hydroxystyrene
structure may be prepared by copolyerization of hydroxystyrene or α-methyl-hydroxystyrene
and acryl-based monomers. The acryl-based monomer may be acrylic esters, methacrylic
esters, acrylamide, methacrylamide, acrylonitrile, or the like. The resin having an
epoxy group may be a novolak-type epoxy resin, a bisphenol-A-type epoxy resin, an
acryl epoxy resin, or the like. The resin having a hydroxyl group and a carboxyl group
may be the resin having a phenolic hydroxyl group or a hydroxystyrene structure to
which a carboxyl group is added, or a copolymer of an acryl-based (or methacryl-based)
monomer having a hydroxyl group and an acryl-based (or methacryl-based) monomer having
a carboxyl group.
[0069] The weight average molecular weight of binder B may be in the range of 500 to 100,000
g/mol. If the weight average molecular weight of the binder B is less than 500 g/mol,
dispersity of the inorganic material in the paste may be reduced. On the other hand,
if the weight average molecular weight of the binder B is greater than 100,000 g/mol,
development speed may be too slow or development may not be performed.
[0070] The amount of the binder B may be in the range of 50 to 95 parts by weight based
on 100 parts by weight of the organic material (the binder, the crosslinking agent
and the photo-acid generator). If the amount of the binder B is less than the range
above, coating properties and dispersity of the paste may be decreased. On the other
hand, if the amount of the binder B is greater than the above range, crosslinking
may not sufficiently occur during the light exposure and desired barrier ribs may
not be obtained.
[0071] The photo-acid generator is a material that generates an acid when exposed to light.
Non-limiting examples of the photo-acid generator include onium salts, sulfonium salts,
organic halogen compounds, naphthoquinone-diazide-sulfonic acids and photoreactive
sulfonic acids.
[0072] The onium salt or the sulfonium salt may include at least one selected from the group
consisting of diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoro arsenate,
diphenyliodium hexafluoro antimonate, diphenylparamethoxyphenylsulfonium triflate,
diphenylparatoluenylsulfonium triflate, diphenylparaisobutylphenylsulfonium triflate,
diphenylpara-t-butylphenylsulfonium triflate, triphenylsulfonium hexafluoro phosphate,
triphenylsulfonium hexafluoro arsenate, triphenylsulfonium hexafluoro antimonate,
triphenylsulfonium triflate and dibutylnaphthylsulfonium triflate, but are not limited
thereto.
[0073] The organic halogen compound may include at least one selected from the group consisting
of tribromoacetophenone, phenyltrihalomethyl-sulfone compound, halomethyl-s-triazine
compound and halomethyl-oxadiazole compound, but is not limited thereto. The naphthoquinone-diazide-sulfonic
acid may include at least one selected from the group consisting of 1,2-naphthoquinone-2-diazide-4-sulfonylchloride
and 1,2-naphthoquinone-2-diazide-5-sulfonylchloride, but is not limited thereto.
[0074] The photoreactive sulfonic acid may include at least one selected from the group
consisting of 1,2-naphthoquinone-2-diazide-4-sulfonic acid ester, 1,2-naphthoquinone-2-diazide-5-sulfonic
acid amide, a compound having a β-keto sulfone group, an ester of nitrobenzylalcohol,
an ester of arylsulfonic acid, an oxime ester compound, a N-hydroxyamide ester compound,
a N-hydroxyimide ester compound, a sulfonic acid ester compound and a benzoic acid
ester compound, but is not limited thereto.
[0075] The amount of the photo-acid generator may be in the range of 0.1 to 5 parts by weight
based on 100 parts by weight of the organic material. If the amount of the photo-acid
generator is less than the above range, a crosslinking reaction may not be sufficiently
performed. On the other hand, if the amount of the photo-acid generator is greater
than the above range, the photo-acid generator absorbs light, thereby decreasing the
photosensitivity.
[0076] The photo-acid generator may further include a sensitizer in order to improve the
photosensitivity. The sensitizer may include at least one selected from the group
consisting of anthracene, phenanthracene, 1,2-benzoanthracene, 1,6-diphenyl-1,3,5-hexatriene,
1,1,4,4,-tetraphenyl-1,3-butadiene, 2,3,4,5-tetraphenylfuran, 2,5-diphenylthiophene,
thioxanthone, 2-chloro-thioxanthone, phenothiazine, 1,3-diphenylpyrazoline, benzophenone,
4-hydroxy-benzophenone, fluorescein and rhodamine, but is not limited thereto. The
amount of the sensitizer may be in the range of 1 to 1000 parts by weight based on
100 parts by weight of the photo-acid generator. If the amount of the sensitizer is
less than the above range, sensitizing effects may be decreased. On the other hand,
if the amount of the sensitizer is greater than the above range, the sensitizer absorbs
the light, thereby decreasing the photosensitivity.
[0077] The crosslinking agent B may be a melamine resin, an urea resin, a guanamine resin,
a glycoluril-formaldehyde resin, a succinyl amide-formaldehyde resin or an ethylene
urea-formaldehyde resin. More specifically, the crosslinking agent B may be a melamine
resin and/or a urea resin for crosslinking reactivity and commercialization. Examples
of the melamine resin and the urea resin are an alkoxymethylated melamine resin and
an alkoxymethylated urea resin. The alkoxymethylated amino resin is prepared by esterifying
a condensation product obtained by reacting melamine or urea with formalin using a
low molecular weight alcohol such as methyl alcohol, ethyl alcohol and propyl alcohol.
[0078] The amount of the crosslinking agent B may be in the range of 5 to 50 parts by weight
based on 100 parts by weight of the organic material. If the amount of the crosslinking
agent B is less than the above range, the crosslinking reaction may not be sufficiently
performed when the organic material is exposed to light, thereby collapsing the pattern
during the developing process. On the other hand, if the amount of the crosslinking
agent B is greater than the range above, dispersibility and printing properties may
deteriorate during a calcination process.
[0079] The photosensitive paste composition according to aspects of the present invention
may further include one or more additives such as, for example, a polymerization inhibitor
and/or an antioxidant that improves preservation properties, a UV ray absorbing agent
that improves resolution, an antifoaming agent that reduces foams in the composition,
a dispersing agent that improves dispersibility, a leveling agent that improves flatness
of membranes during printing, a plasticizer that improves thermal degradation properties,
and a thixotropic agent that provides thixotropy characteristics.
[0080] The solvent may be any solvent that does not decrease dispersibility of the fluoride,
can dissolve the binder A, the binder B, the photoinitiator and the photo-acid generator,
can be easily mixed with the crosslinking agent and other additives, and has a boiling
point of 150 °C or higher. If the boiling point of the solvent is less than 150 °C,
the solvent may be easily evaporated during a preparation process of the composition,
in particular, during a 3-roll mill process, and printing quality may be decreased
since the solvent is quickly evaporated during the printing process. The solvent may
be at least one selected from the group consisting of ethyl carbitol, butyl carbitol,
ethyl carbitol acetate, butyl carbitol acetate, texanol, terpine oil, diethylene glycol,
dipropylene glycol, tripropylene glycol, dipropyleneglycol methyl ether, dipropyleneglycol
ethyl ether, dipropyleneglycol monomethyl ether acetate, γ-butyrolactone, cellosolve
acetate and butylcellosolve acetate, but is not limited thereto.
[0081] The amount of the solvent is not particularly limited, but may be adjusted to provide
a viscosity suitable for printing or coating.
[0082] The photosensitive paste composition according to aspects of the present invention
may be prepared according to the following process.
[0083] First, a fluoride sol is prepared. The fluoride sol may be prepared by preparing
a fluoride precursor by substituting water in a water soluble fluoride gel with an
organic solvent, and dispersing the fluoride precursor in the organic material. The
organic material is previously prepared to a uniform and transparent solution by mixing
each of the organic components and sufficiently stirring the mixture. The prepared
fluoride sol is mixed with an inorganic material to prepare a paste. The paste is
mixed using a planetary mixer PLM, or the like, and mechanically mixed several times
using 3-roll mill. After the 3-roll milling process is completed, a filtering process
is performed using, for example, SUS mesh #400, and degassing is performed using a
vacuum pump to prepare a photosensitive paste composition.
[0084] According to another embodiment of the present invention, barrier ribs for a plasma
display panel (PDP) prepared using the photosensitive paste composition are provided.
The process of preparing the PDP barrier ribs using the photosensitive paste composition
may vary according to types of components in the organic material.
[0085] If the photosensitive paste composition is prepared using the first type of organic
material including the alkali-soluble binder A, the photoinitiator and the crosslinking
agent A, barrier ribs are prepared according to the following process. The photosensitive
paste composition is coated using screen printing or a table coater onto a lower panel
of a PDP on which an address electrode and a dielectric layer have been formed. Most
of the solvent is removed by drying the resultant in a dry oven or an infrared ray
(IR) oven at 80 to 120 °C for 5 to 60 minutes. Then, the dried film is exposed to
light using an ultraviolet ray exposure device having a photomask to initiate crosslinking
reactions on regions exposed to the light. The resultant is developed using a suitable
alkali developing solution such as an Na
2CO
3 solution, a KOH solution, a tetramethyl ammonium hydroxide (TMAH) solution or a monoethanol
amine solution, which are diluted in pure water, at about 30 °C to remove regions
not exposed to the light and to obtain a pattern. Then, a calcination process is performed
in an electric furnace or the like at 500 to 600 °C for 5 to 60 minutes to remove
residual organic materials and sinter the low melting point glass frit. Thus, patternized
barrier ribs may be obtained.
[0086] If the photosensitive paste composition is prepared using the second-type organic
material including the alkali-soluble binder B, the photo-acid generator and the crosslinking
agent B, barrier ribs are prepared in the same manner as in the above process using
the first type of organic material except that when the light exposure process is
performed using the ultraviolet ray exposure device, an acid is generated in the regions
exposed to light instead of crosslinking reactions occurring. The crosslinking reactions
of the second type of organic material occur during a subsequent heat-treatment at
80 to 150 °C for 5 to 60 minutes. Then, subsequent developing and calcination processes
are the same as those described with reference to the first-type organic material.
[0087] According to another embodiment of the present invention, a plasma display panel
(PDP) including the barrier ribs is provided.
[0088] FIG. 1 is a perspective view of a plasma display panel (PDP) according to an embodiment
of the present invention.
[0089] A PDP according to the present invention includes a front panel 110 and a rear panel
120. The front panel 110 includes a front substrate 111, pairs of sustain electrodes
114 including a Y electrode 112 and an X electrode formed on a rear surface of the
front substrate 111 a, a front dielectric layer 115 covering the pairs of sustain
electrodes 114, and a protection layer 116 covering the front dielectric layer 115.
Each of the Y electrode 112 and X electrode 113 includes: transparent electrodes 112b
and 113b formed of ITO, or the like; and bus electrodes112a and 113a including a black
electrode (not shown) to improve brightness and a white electrode (not shown) to provide
conductivity. The bus electrodes112a and 113a are connected to cables arrayed in both
sides of the PDP.
[0090] The rear panel 120 includes a rear substrate 121, address electrodes 122 formed on
the front surface of the rear substrate 121 a to cross the pairs of sustain electrodes,
a rear dielectric layer 123 covering the address electrodes 122, barrier ribs 124
formed on the rear dielectric layer 123 and dividing emission cells 126, and a phosphor
layer 125 disposed in the emission cells. The address electrodes 122 are connected
to cables arrayed in the top and bottom of the PDP.
[0091] Aspects of the present invention will be described in greater detail with reference
to the following examples. The following examples are for illustrative purposes and
are not intended to limit the scope of the invention.
Examples
Preparation of Fluoride Precursor
Preparation Example 1. Preparation of Magnesium Fluoride (MgF2) Precursor
[0092] A magnesium chloride water solution was prepared by dissolving 203.3 g of magnesium
chloride (MgCl
2 • 6H
2O) in 5 L of ion exchanged water, and a potassium fluoride water solution was prepared
by dissolving 188.26 g of potassium fluoride (KF • 2H
2O) in 5 L of ion exchanged water. 10 L of ion exchanged water was added to a 50 L
reactor and the magnesium chloride water solution and the potassium fluoride water
solution were simultaneously added to the reactor at a rate of 10 ml/sec while fiercely
stirring. Then, the mixture was concentrated using a vacuum concentration device until
the volume of the mixture reached 2 L. The concentrated solution was matured by heating
at 95°C for 24 hours to prepare a gel. Then, electrolytes were removed from the gel
using an ultrafiltration membrane, and the resultant was concentrated again using
the vacuum concentration device until the volume of the mixture reached 1 L to prepare
an aqueous magnesium fluoride sol. The aqueous magnesium fluoride sol was treated
in a solvent exchange device using 1 L of diethylene glycol to prepare a magnesium
fluoride precursor dispersed in diethylene glycol.
Preparation Example 2. Preparation of Sodium Magnesium Fluoride (NaMgF3) Precursor
[0093] A sodium magnesium fluoride (NaMgF
3) precursor dispersed in diethylene glycol was prepared in the same manner as in Preparation
Example 1, except that a sodium fluoride water solution, which was prepared by dissolving
126 g of sodium fluoride (NaF) in 5 L of ion exchanged water, was used instead of
the potassium fluoride water solution.
Preparation Example 3 Preparation of Silica-Magnesium Fluoride (SiO2-MgF2 Precursor
[0094] A magnesium chloride water solution was prepared by dissolving 203.3 g of magnesium
chloride (MgCl
2 • 6H
2O) in 5 L of ion exchanged water, a silica sol water solution was prepared by diluting
300 g of silica sol (10 wt%, average particle diameter: 5 nm) in 5 L of ion exchanged
water, and an ammonium fluoride water solution was prepared by dissolving 74.08 g
of ammonium fluoride (NH
4F) in 5 L of ion exchanged water. The prepared silica sol water solution was added
to a 50 L reactor and the magnesium chloride water solution was added to the reactor
at a rate of 10 ml/sec while fiercely stirring. Then, 300 g of 0.1 N hydrochloric
acid solution was added thereto. Then, the ammonium fluoride water solution was added
to the reactor at a rate of 10 ml/sec. Then, a silica-magnesium fluoride precursor
dispersed in diethylene glycol was prepared in the same manner as in Preparation Example
1.
Measuring Physical Properties of Fluoride
[0095] The refractive index (@ 589 nm, 20 °C), specific gravity (@ 20 °C), transmittance
(@ 20 °C) and average particle diameter (@ 20 °C) of the three types of fluoride precursors
prepared according to Preparation Examples 1 to 3 were measured, and the results are
shown in Table 1 below. The transmittance was measured at 500 nm when the thickness
of the fluoride was 1 cm, and the average particle diameter was measured using Photon
Correlation Spectroscopy (PCS).
Table 1
Fluoride |
Refractive index |
Specific gravity |
Transmittance (%) |
Average particle diameter (nm) |
MgF2 |
1.37 |
3.1 |
72 |
15.3 |
NaMgF3 |
1.33 |
2.8 |
68 |
17.5 |
SiO2-MgF2 |
1.41 |
2.9 |
84 |
12.6 |
Preparation of Organic Material
[0096] Organic materials to be mixed with the prepared fluoride precursors and used to prepare
a fluoride sol were prepared according to the following process.
Preparation Example 4. Preparation of Organic Material 1
[0097] An organic mixture including 79.4 wt% of a binder (a novolak resin (prepared by adding
formalin to m-cresol in the presence of an oxalic acid catalyst), weight average molecular
weight: 18,000 g/mol), 19.0 wt% of a crosslinking agent (hexamethoxymethyl-melamine),
and 1.6 wt% of a photo-acid generator (triphenylsulfonium triflate) was prepared.
Organic Material 1 was prepared by adding 30 parts by weight of a solvent (ethylcarbitol)
based on 100 parts by weight of the organic mixture to the organic mixture in order
to control the solubility and viscosity.
Preparation Example 5. Preparation of Organic Material 2
[0098] An organic mixture including 54.0 wt% of a binder (poly(styrene-co-methylmethacrylic
acid) copolymer, weight average molecular weight: 12,000 g/mol, acid value: 180 mgKOH/g),
9.5 wt% of a photoinitiator (2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-1-butanone),
29.5 wt% of a crosslinking agent (bisphenol A modified epoxy diacrylate), and 7.0
wt% of a stabilizing agent for storage (benzotriazole). Organic Material 2 was prepared
by adding 15 parts by weight of a solvent (ethylcarbitol) based on 100 parts by weight
of the organic mixture to the organic mixture in order to control the solubility and
viscosity.
Preparation Example 6. Preparation of Organic Material 3
[0099] An organic mixture including 60.0 wt% of a binder 1 (poly(methyl methacrylate-co-butyl
methacrylate-co-methyl methacrylic acid) copolymer, weight average molecular weight:
12,000 g/mol, acid value 150 mgKOH/g), 2.0 wt% of a binder 2 (hydroxypropyl cellulose,
weight average molecular weight: 80,000 g/mol), 1.5 wt% of a photoinitiator 1 (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one),
0.5 wt% of a photoinitiator 2 (2,4-diethylthioxanthone), 25.0 wt% of a crosslinking
agent 1 (methoxydiethyleneglycol acrylate), 10 wt% of a crosslinking agent 2 (trimethylolpropane
triacrylate), and 1.0 wt% of a stabilizing agent for storage (malic acid). Organic
Material 3 was prepared by adding 20 parts by weight of a solvent (texanol) based
on 100 parts by weight of the organic mixture to the organic mixture in order to control
solubility and viscosity,
Evaluation of Physical Properties of the Organic Materials
[0100] Refractive index and specific gravity of the organic materials prepared according
to Preparation Example 4 to 6 were measured, and the results are shown in Table 2
Table 2
Organic Material |
Refractive index (@ 20°C) |
Specific gravity (@ 20°C) |
Organic Material 1 |
1.55 |
1.14 |
Organic Material 2 |
1.57 |
1.15 |
Organic Material 3 |
1.47 |
1.07 |
Preparation of Fluoride Sol
[0101] Fluoride sols were prepared by respectively dispersing fluoride precursors prepared
according to Preparation Examples 1 to 3 into the organic materials prepared according
to Preparation Examples 4 to 6. In particular, the fluoride sols were prepared by
adding the organic material to a stirring reactor, gradually adding a predetermined
amount of the fluoride precursor to the reactor while stirring, and stirring the reactor
for several hours. The volume ratios used in Preparation Examples 6 to 8 are based
on the volumes without the solvent.
Preparation Example 7. Preparation of Fluoride Sol 1
[0102] The MgF
2 precursor prepared according to Preparation Example 1 and the Organic Material 1
prepared according to Preparation Example 4 were mixed at a volume ratio of 30:70.
The measured refractive index was 1.50.
Preparation Example 8. Preparation of Fluoride Sol 2
[0103] The NaMgF
3 precursor prepared according to Preparation Example 2 and the Organic Material 2
prepared according to Preparation Example 5 were mixed at a volume ratio of 30:70.
The measured refractive index was 1.50.
Preparation Example 9. Preparation of Fluoride Sol 3
[0104] The SiO
2-MgF
2 precursor prepared according to Preparation Example 3 and the Organic Material 3
prepared according to Preparation Example 6 were mixed at a volume ratio of 30:70.
The measured refractive index was 1.45.
Preparation of Photosensitive Paste Composition
[0105] A photosensitive paste composition according to aspects of the present invention
was prepared by mixing Fluoride Sols 1 to 3 prepared according to Preparation Examples
7 to 9 with an inorganic material including a low melting point glass frit and a high
melting point glass frit according to Examples 1 to 3 below. In addition, a photosensitive
paste composition without a fluoride was prepared as shown in Comparative Example
1 below. Here, the volume ratios used in Examples 1 to 3 and Comparative Example 1
are based on the volumes without the solvent.
Example 1. Preparation of Photosensitive Paste Composition 1
[0106] Photosensitive Paste Composition 1 including 45 vol% of Fluoride Sol 1 prepared according
to Preparation Example 7, 50 vol% of a low melting point glass frit (SiO
2-B
2O
3-Al
2O
3-F based glass, amorphous, D
50 = 3.4 µm, refractive index = 1.47), and 5 vol% of a high melting point glass frit
(SiO
2-B
2O
3-Al
2O
3 based glass, amorphous, D
50 = 2.5 µm, refractive index = 1.46) was prepared using a method of preparing the paste
composition.
Example 2. Preparation of Photosensitive Paste Composition 2
[0107] Photosensitive Paste Composition 2 was prepared in the same manner as in Example
1 except that Fluoride Sol 2 prepared according to Preparation Example 8 was used
instead of Fluoride Sol 1 of Preparation Example 7.
Example 3. Preparation of Photosensitive Paste Composition 3
[0108] Photosensitive Paste Composition 3 was prepared in the same manner as in Example
1 except that Fluoride Sol 3 prepared according to Preparation Example 9 was used
instead of Fluoride Sol 1 of Preparation Example 7.
Comparative Example 1. Preparation of Photosensitive Paste without Fluoride
[0109] A photosensitive paste composition without a fluoride including 40 vol% of Organic
Material 3 prepared according to Preparation Example 6, 50 vol% of a low melting point
glass frit (SiO
2-B
2O
3-Al
2O
3-F based glass, amorphous, D
50 = 3.4 µm, refractive index = 1.47), and 10 vol% of a high melting point glass frit
(SiO
2-B
2O
3-Al
2O
3 based glass, amorphous, D
50 = 2.5 µm, refractive index = 1.46) was prepared.
Evaluation of Photosensitive Paste Composition
[0110] Barrier ribs were prepared using the photosensitive paste compositions prepared according
to Examples 1 to 3 and Comparative Example 1 by the following process.
[0111] The photosensitive paste compositions prepared according to Examples 1 to 3 and Comparative
Example 1 were coated onto a 6" glass substrate using a coater, and dried in a dry
oven at 100°C for 30 minutes to form a dry film having a thickness of 180 µm. Then,
light exposure was performed using a high pressure mercury lamp UV exposing unit including
a photomask having a lattice pattern (width:line width = 40 µm (pitch = 160 µm), length:line
width = 40 µm (pitch = 560 µm)) at 300 to 1000 mJ/cm
2. Then, only the glass substrate on which Photosensitive Paste Composition 1 of Example
1 was coated was heat-treated in a dry oven at 120 °C for 10 minutes to perform a
developing process. The other Photosensitive Paste Compositions 2 and 3 and the photosensitive
paste composition without a fluoride were directly developed. The developing process
was performed by spraying a 0.8 wt% sodium carbonate water solution at a nozzle pressure
of 1.5 kgf/cm
2 at 35°C for 200 seconds, and then performing a washing process by spraying pure water
at a nozzle pressure of 1.2 kgf/cm
2 at room temperature for 30 seconds. Then, the glass was dried using an air knife,
and a calcination was performed in an electrical furnace at 560°C for 20 minutes to
form barrier ribs. Then, the formed barrier ribs were evaluated using an optical microscope
and a scanning electron microscope (SEM).
[0112] The results of the evaluation of the barrier ribs are shown in Table 3 below. In
Table 3, the exposure amount was a value showing an optimized pattern, and the color
of barrier ribs was observed with the naked eye.
Table 3
Photosensitive paste composition |
Exposure amount (mJ/cm2) |
Thickness of calcined film |
Upper width |
Lower width |
Color of barrier ribs |
Example 1 |
700 |
122 µm |
48 µm |
55 µm |
white |
Example 2 |
700 |
123 µm |
47 µm |
54 µm |
white |
Example 3 |
600 |
124 µm |
43 µm |
60 µm |
white |
Comparative Example 1 |
400 |
122 µm |
38 µm |
63 µm |
gray |
[0113] The results of Table 3 can be interpreted as follows. The photosensitivity (exposure
amount) depends on the difference between refractive indexes of the fluoride sol and
the inorganic material. That is, the photosensitive paste composition of Example 3
having a small difference of the refractive index has excellent photosensitivity among
those of Examples 1 to 3. In addition, as shown in the results of Table 3, as the
photosensitivity is decreased, the upper width is increased and the lower width is
decreased. This result indicates that light transmittance is decreased and reflection
and scattering are increased as the difference of the refractive index between the
fluoride sol and the inorganic material is increased. According to Table 3, the color
of the barrier ribs including the fluoride was white but the color of the barrier
ribs without the fluoride was gray, and this result indicates that reflectance to
visible rays is different in Comparative Example 1.
Manufacturing Plasma Display Panel (PDP) and Evaluation Properties of the PDP
[0114] A 6" panel was manufactured using the photosensitive paste compositions prepared
according to Examples 1 to 3. In addition, a panel was manufactured using the photosensitive
paste composition according to Comparative Example 1.
[0115] Each 6" panel was manufactured in a pilot line and had specs for a 42" HD panel.
The brightness of the panels was evaluated and the results are shown in Table 4.
Table 4
Photosensitive Paste Composition |
Brightness (lm/W) |
Relative brightness ratio |
Example 1 |
1.33 |
117 |
Example 2 |
1.36 |
119 |
Example 3 |
1.31 |
115 |
Comparative Example 1 |
1.14 |
100 |
[0116] Referring to the brightness results shown in Table 4, if the photosensitive paste
composition of Examples 1 to 3 is used, brightness can be increased by about 15 to
20% compared to the photosensitive paste composition of Comparative Example 1. As
described above, the brightness can be increased since the fluoride increased reflectance
of the barrier ribs.
[0117] According to aspects of the present invention, a plasma display panel (PDP) having
high brightness can be manufactured since the barrier ribs have high reflectance compared
to conventional barrier ribs.
[0118] Although a few embodiments of the present invention have been shown and described,
it would be appreciated by those skilled in the art that changes may be made in this
embodiment without departing from the principles of the invention, the scope of which
is defined in the claims and their equivalents.